Catalytic conversion of hydrocarbons



Patented Mar. 28, 1944 UNITED, STATES PATENT OFFICE CATALYTIC coNvEas oN OF HYDRO- CARBO S Robert E. Burk and Everett 0. Hughes, Cleveland Heights, Ohio, assignors to The Standard Oil C(lninpany, Cleveland, Ohio, a corporation oi o I No Drawing. Application April 29,1941,

Serial No. 390,960

1a claims.

This invention relates to conversion of hydrocarbons, and it is among the objects of the invention to catalytically raise the aromatic content of .hydrocarbons or convert non-benzenoid hydrocarbons to aromatics, and inhibit deposition of coke on the catalyst and facilitatev the heating.

Other objectsand advantages will appear as the The hydrocarbonsto be treated may be of any. desired non-benzenoid character, as aliphatic hydrocarbons or paraflins and olefins and naphthenic hydrocarbons or their mixtures, naphthas,

distillates, etc. l, The catalystor contact material is of peculiar composition, being a gel type coprecipitated combination of oxides of copper, alu-, minum and chromium, the copper oxide being l-lO molpcr'cent, the aluminum oxide 81-60 mol per cent, and the chromium oxide 18-30 mol per cent. The operating temperature for the catalyst is 750." F. and upward, Withthe hydrocarbon feed there may be supplied a hydrocarbon gas of four ,carbon atoms or in some cases less.

Such butane gas may besupplied at the rate of.

1-10 mols per mol of naphtha or the like fed. Preferably, a supply of hydrogen is also provided. This may be in amount.0.1- mols per mol of naphtha or the like. Ofi-gas from the process containing a butane hydrocarbon and hydrogen the foregoing and operating pressure may vary, depending upon other'conditions. Thus, where introducing hy- 'drogen as; the only-additional gas fed into the j a hydroxy compound etc.,' and the undiss'olved' or non-benzenoid portion may be returned to themay conveniently be employed, being returned to the catalyst zone. .Where the arrangement ,of the catalyst involves a series oftrays or beds through which the hydrocarbon feed is passed, it is advantageous to supply the gas additions in successive portions to at least a part of the trays of catalyst, as many as desired. With this kind of catalyst. and asupplyof hydrogen, incipient coke-forming I material is hydrogenated, with exothermic heat generation providing heat in situ also at the catalyst'bedg-r Flow rates of naphtha may be "0.l-10 .liquid volumes per volume of catalyst per hour. At the higher temperature ranges correspondingly shorter contact times may be employed. In operating with supply of hydrogen, the temperature may be slightly higher than those used ordinarily in aromatization. Temperatures of 750-1200 F. are applicable. The

catalyst zone, the pressure may be as higha's 400 lbs. per square inch; where'butaneis employed the pressure may be up to 800 lbs. for instance;v

and commonly the pressure may be 40-400 lbs.

The, productsffrom the catalytic zone, after separating the gases which may be returned in such "amount as desired, may be extracted with a selective solvent or mixture, as for instance liquid sulphur dioxide or a high boiling amine or catalytic zone. The catalyst may be regenerated in situ by shutting. off the feed and applyingto it while the temperature is "at 750-1200 R, an oxygen-containing gas such as air or oxygen which may be diluted with a'suit'able' diluent, for

instance nitrogen. I 7

As an example: A'naphtha from Illinois petroleum is 'passedin contact with a ctr-precipitated gel type oxide catalyst consisting of'2 me] per cent of coppenoxide,f78 mol per cent of aluminum oxide,i;and 20 mol per cent of chromium oxide, at

a temperature of 980 F., and pressure pounds per square inch, and a flowrate of l mol of naphthe. ,(liquid) per volume of catalyst per hour, andhydrogen supplied at the rate of3 mols of hydrogen per molofnaphtha. A yield of 73.3 weight I per .cent .ofgasoline is obtained, having a. Kattwinkel test of 54 and A. S. T. M. octane number (without butane) of 79.7. Operatingwiththe same conditions as foregoing,and adding also1.17. mols of butane gas per molof naphtha, an84.3 j

having an per cent yield. of gasoline 'is obtained A. S. T. M. number of 75.

This application is a continuation, in part and as tocommon subject matter, of our application Serial No. 263,198, filed March 21, 19 39.

Other modes of applyingthe principle of the invention may be employed, change being made as regardsihc detailsdescribed, provided the feaequivalent of such, be employed,

tures stated in anyof the following claims, orthe I :45

tinctly claim as ourinvention: f l. A process of raising the aroma We therefore particularly point, out inane,

of hydrocarbons, which'comprises maintaining at about 750-1200" .F. a gel type catalyst containing 1-10 mol per cent of copper oxide and 81-60 mol per cent of aluminum oxide coprecipitated with 18-30 mol per cent of chromium oxide, and contacting a vaporized naphtha with such catalyst while supplying a butane hydrocarbon and hydroa; mam-- ,hydrocarbons. which comprises about 750-1200 F.

about 750-1200" F. a series or gen in mol ratio of 1-10 and 0. -1?) respectively to 1 of the naphtha, and maintaining superatmospheric pressure.

2. A process of raising the aromatic content of hydrocarbons, which comprises maintaining at about 750-1200 F. a series of bodies of a gel type catalyst containing 1-10 mol per cent of copper oxide and 81-60 mol per cent of aluminum oxide coprecipitated with 18-30 mol per cent of chromium oxide, and passing through the series a vaporized naphtha while supplying to at least a part or the series of catalystbodies a, butane hydrocarbon and hydrogen in mol ratio of'1-10 and 0.1-10 respectively to 1 of the naphtha, and maintaining superatmospheric pressure.

3. A process of raising the aromatic content of hydrocarbons, which comprises maintaining at about 150-1200 F. a gel type catalyst containing 1-10 mol per cent of copper oxide and 81-60 mol per cent of aluminum oxide coprecipitated with 18-30 mol per cent of chromium oxide, and contacting a vaporized naphtha. with the catalyst while supplying a butane gas and hydrogen in mol ratio of 1-10 and 0.1-10 respectively to 1 of the naphtha, and returning oft-gas to the catalyst zone.

4. A process of raising the aromatic content of maintaining at a gel type catalyst containing 1-10 mol per cent oi copper oxide and 81-60 mol per cent of aluminum oxide coprecipitated with 18-30 mol per cent of chromium oxide, and contacting a vaporized naphtha with the catalyst while supplying a butane gas in mol ratio or 1-10 to 1 or the naphtha, and returning non-benzenoid hydrocarbons from the product to the catalyst.

5. A process of raising the aromatic content of hydrocarbons, which comprises maintaining at type catalyst containing 1-10 mol per .cent of copper oxide and 81-60 mol 'per cent or aluminum oxide coprecipitated with 18-30 mol per cent of chromium oxide, and passing through the series a vaporized naphtha while supplying to at least a part or the series of catalyst bodies hydrogen in mol ratio 0.1- to 1 of the naphtha, and

maintaining superatmosphericjpre'ssure.

6. A process of raising the aromatic content of hydrocarbons, which comprises maintaining at about 750-1200" F. a gel type catalyst containing 1-10 mo] per cent of copper oxide and 81-60 mol per cent of aluminum oxide coprecipitated with 18-30 mol per cent of chromium oxide, and passing in contact with such catalyst an aromatma'ole non-benzenoid hydrocarbon, while supplying a butane gas and hydrogen in mol ratio of 1-10 and 0.1-10 respectively to 1 of the hydrocarbon, and maintaining superatmospheric pressure.

7. A process of raising the aromatic content of hydrocarbons, which comprises maintaining at about '750-1200 F. a series of bodies of a gel type catalyst containing 1-10 mol per cent of copper oxide and 80-60 mol per cent of aluminum mium oxide, and aromatizable non-benzenoid hydrocarbon, while supply'ingto at least a part of the serlesof catabodies a butane hydrocarbon and hydrogen the hydrocarbon, and maintaining superatmospheric pressure.

8. A process of raising the aromatic content of hydrocarbons, which comprises maintaining at about 750-1200 F. a gel type catalyst containing 1-10 mol per cent or copper oxide and 80-60 mol per cent of aluminum oxide coprecipitated with 18-30 mol per cent of chromium oxide, and contacting an aromatizable non-benzenoid hydrocarbon with the catalyst, while supplying a butane hydrocarbon and hydrogen in mol ratio bodiesfot a gel v oxide coprecipitated with 18-30 mol per cent of chropassing throughthe series an of 1-10 and 01-10 respectively to 1 of the hydrocarbon.

9. A process of raising the aromatic content of hydrocarbons, which comprises maintaining at elevated temperature a gel type catalyst containing 1-10 mol per cent of copper oxide and 81-60 mol per cent of aluminum oxide coprecipitated with 18-30 mol per cent of chromium oxide, and passing an aromatizable non-benzenoid hydrocarbon in contact with such catalyst, while supplying a. butane hydrocarbon and hydrogen in molratio of 1-10 and 0.1-10 respectively to 1 of the hydrocarbon, and returning off-gas to the catalyst zone.

10. A process or raising the aromatic content of hydrocarbons, which comprises maintaining at elevated temperature a gel type catalyst containing 1-10 mol per cent of copper oxide and 81-60 mol per cent of aluminum oxide coprecipitated with 18-30 mol per cent of chromium oxide, and passing an aromatizable non-benzenoid hydrocarbon in contact with such catalyst, while supplying a butane gas and hydrogen in mol ratio of 1-10 and 0.1-10 respectively to 1 of the hydrocarbon, and returning non-benzenoid hydrocarbons from the product to the catalyst.

11. A process of raising the aromatic content of hydrocarbons, which comprises maintaining at elevated temperature a gel type catalyst containing 1-10 mol per cent 0!. copper oxide and 81-60 mol per cent '0! aluminum oxide coprecipitated with 18-30 mol per cent of chromium oxide, and passing an aromatizable non-benzenoid hydrocarbon in contact with such catalyst, while supplying hydrogen in mol ratio or 0.1-10 to 1 of the hydrocarbon, and maintainingsuperatmospheric pressure.

12. A process of converting hydrocarbons to aromatics, which comprises subjecting non-benzenoid hydrocarbons in the presence of a portion of ofl-gas returned from the process to the action, at 750-1200 F., of a contact mass characterized by 1-10 mol per cent of copper oxide with 60-81 mol per cent of gel type aluminum oxide which is coprecipitated with 18-30 mol per cent of chromium oxide.

13. A process of converting hydrocarbons to aromatics, which comprises subjecting a nonbenzenoid hydrocarbon containing naphtha in the presence of a portion or oil-gas retumed from the process to the action, at 750-1200 F., of a contact mass characterized by 1-10 mol per cent of copper oxide with 60-81 mol per cent or gel type aluminumoxide which is coprecipitated with 18-30 mol per cent of chromium oxide.

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